Amino/polyoxyalkylenated polydioganosiloxanes

ABSTRACT

Novel organofunctional polydiorganosiloxanes containing amino and polyoxyalkylene groups, well adapted as surfactants, dispersants or additives to textile rinsing softening compositions, or to solid antifoams for washing powders, have the formula: ##STR1##

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to novel organofunctionalpolydiorganosiloxanes comprising amino and polyoxyalkylene groups, to aprocess for preparing such novel polydiorganosiloxanes, and to the enduses thereof.

2. Description of the Prior Art

A wide variety of polydiorganosiloxanes containing an amino group or apolyoxyalkylene group are described in the literature, as are the endapplications/uses thereof, in particular, their use in detergentcompositions, antifoams, polyurethane foam additives, glazingcompositions (polishes), and the like.

GB-A-1,409,741 and GB-A-1,409,742 describe the synthesis ofamino-functional polydiorganosiloxanes containing alkoxy groups. Thesepolymers are prepared by the partial reaction of allylamine with apolydiorganosiloxane bearing a ≡SiH hydride group in the presence of aplatinum-based catalyst. The residual ≡SiH groups are then reacted withan alcohol, for example, isopropanol. These materials are used asadditives for detergent-resistant glazing compositions.

U.S. Pat. No. 4,184,004 describes a polydiorganosiloxane containing anepoxy group and a polyoxyalkylene group and its use as a textilesoftener.

GB-A-2,201,433 describes the use of a polydiorganosiloxane containing anammonium group and a polyoxyalkylene group as an additive to a detergentor rinsing composition.

EP-A-58,493 relates to the use of a combination of three functionalpolydiorganosiloxanes (A), (B) and (C) for the treatment of textilefibers, (A) containing both amino groups and polyoxyalkylene groups.Although the definition of (A) is extremely broad, EP-A-58,493specifically describes only one particular oil (A) of the formula:

    Me(Me.sub.2 SiO).sub.130 (MeFSiO).sub.3 (MeGSiO).sub.10 SiMe.sub.3

where

F=--(Ch₂)₃ --NH(CH₂)₂ NH₂

G=--(CH₂)₃ O(C₂ H₄ O)₁₀ H.

SUMMARY OF THE INVENTION

A major object of the present invention is the provision of improvedpolydiorganosiloxanes comprising amino and polyoxyalkylene groups thatare easily produced.

Another object of the present invention is the provision of novelpolydiorganosiloxanes of the above type that are stable in an aqueousmedium, are hydrophilic in nature, are readily emulsified ormicroemulsified, and which can, in certain cases, be water-soluble ordispersible in aqueous media.

Still another object of this invention is the provision of novelpolydiorganosiloxanes of the above type which are useful as surfactantsand additives in detergent compositions, especially in rinsingcompositions for linens, and also additives for silicone antifoamcompositions.

Briefly, the present invention features novel polydiorganosiloxanescomprising amino and polyoxyalkylene groups and having the averageformula (1): ##STR2## which the radicals R are each a C₁ -C₄ alkyl,phenyl or 3,3,3-trifluoropropyl radical, at least 80% of the number ofradicals R being methyl radicals; X is a single covalent bond or adivalent radical of the formula (2):

    --O--CH.sub.2 --CH(OH)--CH.sub.2 --NH--W--                 (2);

Y is a single covalent bond or a divalent radical of the formula (3):##STR3## with the proviso that, if p=O and X is a covalent bond, Y is aradical of formula (3); m is a number ranging from 1 to 25, andpreferably from 1 to 10; n is a number ranging from 1 to 25, andpreferably from 1 to 10; p is a number ranging from 0 to 15, andpreferably from 1 to 5; g is a number ranging from 5 to 500, andpreferably from 10 to 400; a is a number ranging from 0 to 150; b is anumber ranging from 0 to 150; a+b ranges from 5 to 200; W is a divalenthydrocarbon radical having from 1 to 6 carbon atoms, such as --CH₂,--(CH₂)₂ --, --CH₂)₃, --CH₂)₆, --CH₂ --, -- CH₂)₂, --CH₂)₃, --CH₂)₆,##STR4## with --(CH₂)₂ being the preferred radical; R' is a hydrogenatom, a C₁ -C₆ alkyl radical, a C₁ -C₆ acyl radical or a phenyl radical,with R' preferably being a methyl radical, like the radical R; and R" isa linear or branched C₁ -C₆ alkyl radical, preferably isopropyl andisobutyl.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION

More particularly according to the present invention, by varying theratio a/b and the sum a+b, the hydrophilic nature and hydrophobic natureof the polymers of formula (1) can be readily modified.

In the case where X is a covalent bond and Y a divalent radical offormula (3), the polymers of formula (1) may be advantageously preparedin the following manner:

The starting material is a hydropolydiorganosiloxane of the formula:

    R.sub.3 SiO(RHSiO).sub.c (R.sub.2 SiO).sub.q SiR.sub.3     (4)

in which R and g are as defined above and c=m+n+p.

In a first step, the SiH groups of the polymer (4) are partiallyhydrosilylated by adding a suitable amount of allylamine in the presenceof a hydrosilylation catalyst, preferably a platinum-based catalyst.

The platinum-based catalysts suitable for carrying out thehydrosilylation reaction of the polymers of formula (4) are extensivelydescribed in the literature; particularly exemplary are the complexes ofplatinum with an organic material described in U.S. Pat. Nos. 3,159,601,3,159,602 and 3,220,972 and in European Patents A-57,459, A-188,978 andA-190,530, and the complexes of platinum with vinyl organopolysiloxanedescribed in U.S. Pat. Nos. 3,419,593, 3,377,432 and 3,814,730.

To react the polymer of formula (4) with allylamine, an amount ofplatinum-based catalyst, calculated in terms of the weight of platinummetal, ranging from 5 to 600 ppm, and preferably from 10 to 200 ppm,based on the weight of SiH-containing polymer of formula (4), istypically employed.

The hydrosilylation reaction can be carried out in bulk, or in avolatile organic solvent such as toluene, heptane, xylene,tetrahydrofuran, tetrachloroethylene and white spirits.

It is generally desirable to heat the reaction mixture to a temperatureranging from 30 to 200° C. for the time required for the reaction toproceed to completion. Moreover, it is desirable to add the allylaminedropwise to the polymer of formula (4) dissolved in an organic solvent,and preferably at the reflux temperature of the solvent.

The solvent is then optionally removed, for example by distillationunder reduced pressure. However, the resulting polymer solution may bedirectly used for the second step of the process.

The polymer obtained corresponds to the formula: ##STR5## wherein R, mand q are as defined above and d=n+p.

The polymer of formula (5) can include, by way of impurities, a smallamount of structural units of the formulae: ##STR6##

In a second step, all or part of the residual ≡SiH groups of the polymerof formula (5) are hydrosilylated with an unsaturated polyoxyalkylene ofthe formula: ##STR7## wherein a, b and R' are as defined above.

This second step is similar to the first step. It is preferable toconduct the operation in an organic solvent medium, preferably the sameas that used in the first step, and the starting material is then thesolution of the polymer (5) obtained at the end of the first step. It isthen not necessary to add a platinum-based catalyst, which is alreadypresent in such solution.

The solvent is removed, for example, by distillation under reducedpressure. The polymer obtained may be purified, for example, by passingsame through an absorbent silica column.

If this polymer does not contain residual ≡SiH groups, it corresponds tothe formula (1) in which p=O. If this polymer contains residual ≡SiHgroups, they are reacted with an alcohol of formula R"OH, with R" beingas defined above, in the presence of a catalyst such asdiethylhydroxylamine, according to British Patents A-1,409,741 andA-1,409,742 noted above.

Of course, the units of the formulae: ##STR8## may persist, by way ofimpurities, in the polymer of formula (1).

These units may be blocked by reaction with an alcohol of formula R"OH,giving units of the formulae: ##STR9##

To prepare the polymers of formula (1) in which X is a radical offormula (2), the starting material is a polymer of formula (4) asdefined above, on which, during a first step, a partial hydrosilylationis carried out by means of an unsaturated polyoxyalkylene of theformula:

    CH.sub.2 ═CHCH.sub.2 Y--OC.sub.2 H.sub.4).sub.a (OC.sub.3 H.sub.6).sub.b OR'                                        (7)

in which Y, a, b and R' are as defined above, to obtain the polymer ofthe formula: ##STR10## in which R, R' , Y, n, g, a and b are as definedabove and e=m+p.

In a second step, the polymer of formula (8) is completelyhydrosilylated with allyl glycidyl ether of the formula: ##STR11##

The polymer obtained, which may be prepared according to U.S. Pat. No.4,184,004 noted above, is optionally reacted with an alcohol R"OH in thecase where residual ≡SiH groups remain. The polymer is then reacted witha molar excess of a diamine of formula H₂ NWNH₂, with W being as definedabove, and the polymer of formula (1) is thereby obtained.

The polymer of formula (1) is substantially linear, being composedalmost exclusively of units M: (R₃ SiO_(1/2)) and D: (R₂ SiO).

However, up to 10 mol % of units T: (RSiO_(3/2)) may be present.

The polymer of formula (1) may be water-soluble, dispersible in water orinsoluble in cold or hot water. In general, the water-solubility isincreased by increasing the weight content of polyoxyalkylene groups inthe polymer and varying the ratio a/b and the sum a+b.

The polymer of formula (1) can, hence, depending on the case, be used asis, dissolved in an organic solvent, in aqueous solution or dispersion,or in emulsion and microemulsion form.

The polymers according to the invention are especially useful fortreating glass fibers and organic fibers (sizes), for textile treatmentand softening, as surfactants, water-repellent agents, mold-releaseagents, lubricants, additives for organic polymers, especially PVC,lubricants for textile fibers, additives for detergent-resistantpolishes and antifoam and defoaming agents.

The polymers of formula (1) are especially useful in bulk, or dissolvedin an organic solvent, for treating textile fibers. They are thenpreferably used in combination with anα,ω-(dihydroxy)polydiorganosiloxane oil having a viscosity ranging from100 to 150,000 mPa.s at 25° C., in which the organic radical ispreferably methyl, optionally in the presence of a condensation catalystsuch as a tin salt.

From 10 to 1,000 parts of hydroxylated oil are then used per 100 partsof polymer (1).

The polymers according to the invention are more especially useful, onthe one hand as dispersants in solid antifoams for washing powders, and,on the other, as a silicone additive in textile rinsing compositions,optionally in combination with an organic and preferably a cationicsurfactant.

The solid antifoam for washing powder contains:

(i) 100 parts of a matrix selected from among polyethylene glycol, apolyoxyethylene/polyoxypropylene copolymer, a solid surfactant such assorbitan mono- or tristearate and a solid wax, as well as the variouspossible mixtures thereof;

(ii) 1? to 80 parts of a dispersion of pyrogenic or precipitated silicain a silicone oil, generally a polydimethylsiloxane oil; and

(iii) 1 to 20 parts of the polymer of formula (1).

This antifoam is prepared in the following manner:

The silica/polydimethylsiloxane oil dispersion is mixed in the heatedstate in a molten matrix which is either soluble, or insoluble, ordispersible in water, adding the dispersant which is the polymer offormula (1) according to the invention.

The molten dispersion is then cooled and the resulting solid mass isthereafter ground to produce a powder which flows well.

According to the second application, to which the invention relates morespecifically, the polymer of formula (1) is used as a silicone additivein a rinsing composition containing an aqueous dispersion of at leastone cationic organic surfactant suitable for textiles and which softenstextiles, as described in FR-A-2,318,268, for example, which isgenerally a quaternary ammonium salt containing two long-chain,generally C₁₂ -C₂₀, alkyl radicals.

At least one polymer of formula (1) is added, depending on theparticular case, to the cationic surfactant in the form of an emulsion,a dispersion or an aqueous solution. The weight ratio of the organicsurfactant to the polymer (1) ranges from 3:1 to 1:20.

The rinsing bath is then effective at a content of organic surfactantplus polymer of formula (1) of from 15 to 600 ppm, including at least 8ppm of polymer of formula (1).

In order to further illustrate the present invention and the advantagesthereof, the following specific examples are given, it being understoodthat same are intended only as illustrative and in nowise limitative.

In said examples to follow, as in the above description, all parts andpercentages are given by weight, unless otherwise indicated.

EXAMPLE 1

(i) 114.4 parts of a hydrogenopolydimethylsiloxane of average formulaMe₃ SiO(Me₂ SiO)₁₅ (MeHSiO)₃ SiMe₃ (Me=CH₃);

(ii) 100 parts of toluene; and

(iii) 0.016 part of bis(diethyl sulfide)platinum dichloride were heatedto reflux to remove all of the water; and

(iv) 5 parts of allylamine were added dropwise over one hour at reflux.

A sample of the reaction mixture was then withdrawn and had aneutralization equivalent of 1,554 and an infrared spectrumdemonstrating the presence of an ≡SiH group.

136 parts of the poly(oxyalkylene) of the average formula: ##STR12##obtained by the reaction of suitable amounts of ethylene oxide andpropylene oxide with allyl glycidyl ether in the presence of sodiummethanolate, were then added to the reaction mixture.

This addition was carried out under reflux over 50 minutes, and thereaction mixture was heated under reflux for an additional 1 hour, 30minutes.

The solvent was removed under vacuum at 100° C. and a yellow oil ofviscosity 100 mPa.s at 25° C. was thereby obtained. This oil containedno residual ≡SiH groups and had a neutralization equivalent of 3,480.The oil was dispersible in water and had a cloud point of 53° C.

EXAMPLE 2

(i) 142 parts of hydrogenopolydimethylsiloxane of average formula:MeSiO(Me₂ SiO)₁₅ (MeHSiO)₃ SiMe₃ ;

(ii) 100 parts of toluene; and

(iii) 0.022 part of bis(diethyl sulfide)platinum dichloride were mixedand heated to reflux; and

(iv) 3 parts of allylamine were added dropwise over 30 minutes atreflux.

A sample of the reaction mixture was then withdrawn. After removal ofthe solvent, this sample had a neutralization equivalent of 2,852.

The IR spectrum demonstrated the presence of residual ≡SiH groups.

195 parts of the polyoxyalkylene used in Example 1 were added at refluxover 5 minutes.

A cloudy solution was obtained, which became clear after refluxing for 2hours, 30 minutes.

After this period, all the residual ≡SiH groups had disappeared. Afterremoval of the toluene, an oil of viscosity 380 mPa.s at 25° C. wasobtained, having a neutralization equivalent of 7,400.

This oil was dispersible in water with a cloud point of 59° C.

EXAMPLE 3

The procedure of Example 1 was repeated exactly, except that thestarting mixture comprised:

(i) 144.8 parts of a hydrogenopolydimethylsiloxane oil of averageformula: Me₃ SiO(Me₂ SiO)₁₄ (MeHSiO)₄ SiMe₃ ;

(ii) 100 parts of toluene;

(iii) 3 parts of allylamine; and

(iv) 0.016 part of the same platinum-based catalyst.

The sample withdrawn had a neutralization equivalent of 2,900.

270 parts of the same polyoxyalkylene were added, to finally obtain anoil of viscosity 302 mPa.s at 25° C., a neutralization equivalent of9,100 and a cloud point of 52° C.

EXAMPLE 4

The procedure of Example 1 was repeated exactly, except that thestarting mixture comprised:

(i) 477.8 parts of a hydrogenopolydimethylsiloxane of average formula:Me₃ SiO(Me₂ SiO)₁₅ (MeHSiO)₃.1 SiMe₃ ;

(ii) 400 parts of toluene;

(iii) 0.0594 part of the same platinum-based catalyst; and

(iv) 19.95 parts of allylamine, followed by the addition of:

(v) 577 parts of the same polyoxyalkylene.

The oil obtained had a viscosity of 165 mPa.s at 25° C., aneutralization equivalent of 3,390 and a cloud point of 52° C.

EXAMPLE 5

In a mixer, a dispersion was prepared by mixing:

(i) 95 parts of a trimethylsiloxy-blocked polydimethylsiloxane oil; and

(ii) 5 parts of a hydrophobic silica, DEGUSSA SIPERNA® D10, marketed byDEGUSSA.

40 parts of this dispersion were then mixed in the molten state with 55parts of polyethylene glycol of molecular weight 6,000 and 5 parts ofthe silicone oil obtained in Example 1.

The mixture obtained was cooled rapidly by spreading into a thin solidfilm.

This film was ground to a very fluid, fairly crude powder which flowedwell.

The powder consisted of particles of the silicone oil/silica dispersionmicroencapsulated by a solid matrix of polyethylene glycol, whichdispersed readily in an aqueous medium to provide a very good antifoam.

COMPARATIVE EXAMPLE 6

The procedure of Example 5 was repeated exactly, except that the oil ofExample 1 was not introduced.

The solid product obtained was sticky and could not be ground into apowder which flowed well.

EXAMPLE 7

The procedure of Example 5 was repeated exactly, except that, in placeof polyethylene glycol, the same amount of sorbitan stearate SPAN® 65,marketed by ICI, was used.

After grinding, a powder which flowed well, dispersing readily in hotwater and cold water and forming an efficient antifoam, was obtained.

EXAMPLE 8

The foam height profile of a commercial washing powder for automaticwashing machines, not containing an antifoam, was established as afunction of time and temperature, using a ZANUSSI® FL811 front-openingwashing machine.

The same profile was established after incorporation of 0.2% of the oilof Example 1. A substantial decrease in the foam level was observed,especially upon completion of the high temperature/high agitationwashing cycle.

EXAMPLE 9

162.05 g of a hydrogenopolydimethylsiloxane of the average formula:

    Me.sub.3 SiO(Me.sub.2 SiO).sub.8 (MeHSiO).sub.3.1 SiMe.sub.3

were dried by refluxing in toluene for 90 minutes. 42 ppm (calculatedwith respect to the weight of the silicone oil) of the platinum-basedcatalyst used in Example 1 were added, followed by 9.98 g of allylamineadded dropwise over 1 hour.

The reaction mixture was brought to reflux for one additional hour and asample was withdrawn. This sample, from the which the toluene wasremoved, required 13.05 ml of N/10 hydrochloric acid for neutralization.256.4 g of a polyoxyalkylene of the formula: ##STR13## were then reactedat reflux for 30 minutes, the solvent then being removed at reflux for 2hours. The residual ≡SiH content was 28% with respect to the initialcontent. Refluxing was continued for an additional 2 hours, resulting ina residual ≡SiH content of 19%. The reaction mixture was cooled to 110°C. and 42 ppm of platinum-based catalyst were added. The mixture washeated and brought to reflux again for 2 hours.

The residual ≡SiH content was 8%.

Refluxing for 3 hours, 30 minutes, removed all of the residual ≡SiHgroups.

The reaction mixture was cooled to 80° C.

2 g of bentonite, 2 g of active charcoal and 2 g of water were addedwhile the mixture was stirred for 90 minutes. The latter was filtered onCELITE® and the solvent was removed under reflux.

An oil having the following characteristics was obtained:

(a) % residual ≡SiH: 0;

(b) amine equivalent: 3,040;

(c) viscosity at 25° C.: 172 mPa.s;

(d) cloud point: 49° C.

(solution cloudy at 15° C., which was completely clear at 25° C.).

While the invention has been described in terms of various preferredembodiments, the skilled artisan will appreciate that variousmodifications, substitutions, omissions, and changes may be made withoutdeparting from the spirit thereof. Accordingly, it is intended that thescope of the present invention be limited solely by the scope of thefollowing claims, including equivalents thereof.

What is claimed is:
 1. A polydiorganosiloxane comprising amino andpolyoxyalkylene groups and having the average formula (1): ##STR14## inwhich the radicals R are C₁ -C₄ alkyl, phenyl or 3,3,3-trifluoropropylradicals, at least 80% of the number of the radicals R being methylradicals; X is a single covalent bond Y is a divalent radical of theformula (3): ##STR15## m is a number ranging from 1 to 25; n is a numberranging from 1 to 25; p is a number ranging from 0 to 15; g is a numberranging from 5 to 500; a is a number ranging from 0 to 150; b is anumber ranging from 0 to 150; a+b ranges from 5 to 200; R' is a hydrogenatom, a C₁ -C₆ alkyl radical, a C₁ -C₆ acyl radical or a phenyl radical;and R" is a linear or branched C₁ -C₆ alkyl radical.
 2. Thepolydiorganosiloxane as defined by claim 1, wherein R and R' are methylradicals.
 3. The polydiorganosiloxane as defined by claim 1, wherein mranges from 1 to 10; n ranges from 1 to 10; p ranges from 1 to 5; and granges from 10 to
 400. 4. A process for the preparation of thepolydiorganosiloxane as defined by claim 1 comprising partiallyhydrosilylating a corresponding hydrogenopolydiorganosiloxane withallylamine, next hydrosilylating all or a fraction of the residual ≡SiHgroups with a polyoxyalkylene compound of the formula: ##STR16## andthen reacting any residual ≡SiH groups with an alcohol of the formulaR"OH.
 5. In a process for the surface treatment of textile fibers, theimprovement which comprises utilizing as the treatment agent therefore,the polydiorganosiloxane as defined by claim 1.